EP0874807B1 - Process for the preparation of methoxyminophenylglyoxylic acid derivatives - Google Patents

Process for the preparation of methoxyminophenylglyoxylic acid derivatives Download PDF

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EP0874807B1
EP0874807B1 EP96939832A EP96939832A EP0874807B1 EP 0874807 B1 EP0874807 B1 EP 0874807B1 EP 96939832 A EP96939832 A EP 96939832A EP 96939832 A EP96939832 A EP 96939832A EP 0874807 B1 EP0874807 B1 EP 0874807B1
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acid
formula
preparation
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EP0874807A1 (en
EP0874807B2 (en
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Jean-Marie Assercq
Richard Breitschuh
Werner Pfaff
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Bayer CropScience AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
    • C07C235/76—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C235/78—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/60—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by carboxyl groups

Definitions

  • the present invention relates to a process for the preparation of o-chloromethylphenylmethoximinoglyoxylic acid esters of formula I wherein R is C 3 -C 8 alkyl, in which process o-chloromethylphenylglyoxylic acid amide of formula III is, concurrently,
  • Both reaction steps are conveniently carried out in the temperature range from 20° to 70°C, preferably from 40° to 70°C.
  • the O-methylhydroxylamine is used as such, but preferably as salt.
  • Preferred salts are suitably those with mineral acids, such as hydrohalic acid, sulfuric acid, phosphoric acid, nitric acid and the like, but also with organic acids, such as sulfonic acids (methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid and the like), acetic acid, trichloroacetic acid, lactic acid, maleic acid, oxalic acid, and others.
  • mineral acids such as hydrohalic acid, sulfuric acid, phosphoric acid, nitric acid and the like
  • organic acids such as sulfonic acids (methanesulfonic acid, ethanesulfonic acid, benzenes
  • the compounds of formula I are valuable intermediates for obtaining E-configurated fungicides of the methoximinophenylglyoxylic acid ester series of formula IV, of which the methyl esters, in particular, are of high economic importance (EP-254426, EP-460575, EP-463488, EP-472300, EP-299694, EP-253213, WO-95/18789, WO-95/21153, and others).
  • the methoximinophenylglyoxylic acid ester correspond to the general formula IV wherein
  • Aryl is phenyl or naphthyl, preferably phenyl.
  • the o-chloromethylphenylmethoximinoglyoxylic acid esters of formula I can have the E-configuration, or a Z-configuration, at the imino double bond desirable for the biological activity.
  • a very special advantage of the present synthesis of compounds of formula I is that by this process, which proceeds via a long-chain ester, the E-configuration is formed almost exclusively (E/Z ratio higher than 90 : 10).
  • suitable alkanols for obtaining intermediates of formula I according to this invention are n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol as well as n-pentanol, n-hexanol, n-heptanol, n-octanol and the corresponding isomers thereof.
  • the C 5 -C 6 alkanols in all isomeric forms are preferred, in particular n-pentanol.
  • the esterification of compound III or of the corresponding oxime can be carried out in conventional manner under acid reaction conditions, e.g. by adding sulfuric acid or by introducing HCl gas into the reaction medium.
  • the C 3 -C 8 alkanol serving the esterification can be used in excess and can also serve as only solvent or diluent. It can also be reacted in admixture with one or more than one inert diluent.
  • Suitable diluents are, for example, hydrocarbons or halogenated hydrocarbons, typically hexane, heptane, octane, chloroform, dichloroethane; aromatic hydrocarbons or aromatic halogenated hydrocarbons, typically toluene, xylene, chlorobenzene, dichlorobenzene; or ethers such as dioxane, tetrahydrofuran, diisopropyl ether; ketones such as acetone, methyl isobutyl ketone, cyclopentanone; or mixtures thereof.
  • hydrocarbons or halogenated hydrocarbons typically hexane, heptane, octane, chloroform, dichloroethane
  • aromatic hydrocarbons or aromatic halogenated hydrocarbons typically toluene, xylene, chlorobenzene, dichlorobenzene
  • ethers such as dioxane, te
  • the esterification can be carried out either direct with exclusion of water or under aqueous conditions via prior hydrolysis.
  • the hydrolysis of the amide III is preferaby carried out in the presence of stoichiometric amounts of water in the form of the corresponding aqueous concentrated hydrohalic acid, preferably in hydrochloric acid, at a concentration of 25% or more.
  • the alkanolysis can be catalysed by small amounts of sulfuric acid or phosphoric acid. Said alkanolysis is carried out in the temperature range from -10° to +120°C, preferably from 0° to 50°C and, particularly preferably, from 20° to 50°C in the presence of the C 3 -C 8 alkanol.
  • hydrolysis and esterification proceed in one single reaction step of the alkanolysis.
  • reaction of the keto group in the compound of formula III with O-methylhydroxylamine or its salt can be carried out before or after this alkanolysis step of compound III, but is preferably carried out concurrently. It is an essential feature of this invention that the conversion of III to I can be carried out in one single process step.
  • the invention also relates to a combined process for the preparation of o-chloromethylphenylmethoximinoglyoxylic acid esters of formula I by
  • the process of this invention has the surprising advantage of affording the novel amide III in crystalline form in high yield and purity.
  • the use of pure amide III for preparing the compounds of formula I constitutes another advantage of the present process.
  • the compounds of formula I are useful as intermediates containing a reactive o-chloromethyl group for preparing pesticides.
  • pesticides can be fungicides, insecticides, acaricides, nematicides or herbicides such as are disclosed in EP-A-254426, EP-A-460575, EP-A-463488, EP-A-472300, EP-A-299694, EP-A-253213, WO-95/18799, WO-95/21153 as well as in other publications.
  • reaction mixture is added over 30 minutes to a mixture of 400 ml of water and 250 ml of toluene at room temperature, the pH being adjusted to 5 with concentrated hydrochloric acid.
  • the aqueous phase is extracted twice with 150 ml of toluene.
  • the combined organic phases are washed with 150 ml of water.
  • the solvent is distilled off under vacuum at 60°C. 227 g of crude oil are obtained having a 83% content.
  • reaction mixture is added over 30 minutes to a mixture of 400 ml of water and 250 ml of toluene at room temperature, the pH being adjusted to 5 with concentrated hydrochloric acid.
  • the aqueous phase is extracted twice with 150 ml of toluene.
  • the combined organic phases are washed with 150 ml of water.
  • the solvent is distilled off under vacuum at 60°C. 227 g of crude oil are obtained having a 83% content.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

The present invention relates to a process for the preparation of o-chloro-methylphenylmethoximinoglyoxylic acid esters of formula (I), wherein R is C3-C8 alkyl, in which process o-chloromethylphenylglyoxylic acid amide of formula (III) is, in any order or concurrently, a) oximated with O-methylhydroxylamine and b) esterified under acid conditions with an R-OH alcohol, wherein R is C3-C8 alkyl. A process for the preparation of compound (III) is also described, as well as the use of the compounds of formula (I) in the preparation of fungicides.

Description

The present invention relates to a process for the preparation of o-chloromethylphenylmethoximinoglyoxylic acid esters of formula I
Figure 00010001
wherein R is C3-C8alkyl, in which process o-chloromethylphenylglyoxylic acid amide of formula III
Figure 00010002
is, concurrently,
  • a) oximated with O-methylhydroxylamine and
  • b) esterified under acid conditions with a C3-C8alkanol.
    • Both reaction steps are conveniently carried out in the temperature range from 20° to 70°C, preferably from 40° to 70°C. The O-methylhydroxylamine is used as such, but preferably as salt. Preferred salts are suitably those with mineral acids, such as hydrohalic acid, sulfuric acid, phosphoric acid, nitric acid and the like, but also with organic acids, such as sulfonic acids (methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid and the like), acetic acid, trichloroacetic acid, lactic acid, maleic acid, oxalic acid, and others.
    Meanwhile a preparation method has been published (WO 95/34526) wherein a phenylacylcyanide react with an alcohol (Pinner-reaction) to the ester, which in tum can be converted with hydroxylamine and methylation or with 0-methylhydroxylamine to the oximether of formula I herein.
    The compounds of formula I are valuable intermediates for obtaining E-configurated fungicides of the methoximinophenylglyoxylic acid ester series of formula IV, of which the methyl esters, in particular, are of high economic importance (EP-254426, EP-460575, EP-463488, EP-472300, EP-299694, EP-253213, WO-95/18789, WO-95/21153, and others).
    The methoximinophenylglyoxylic acid ester correspond to the general formula IV
    Figure 00020001
    wherein
  • R is C5-C8alkyl, and
  • A is -N=CR2R3, and
  • R2 = hydrogen, C1-C4alkyl, C1-C4haloalkyl, C3-C6cycloalkyl;
  • R3 = C1-C6alkyl, aryl-C1-C4alkyl, heteroaryl-C1-C4alkyl, C2-C6alkenyl, aryl-C2-C6alkenyl, heteroaryl-C2-C6alkenyl, C3-C6cycloalkyl, heteroaryl, aryl, or aryl which is substituted by one to three halogen, C1-C4alkyl, C1-C4haloalkyl.
    • Particularly preferred compounds of formula IV are those, wherein
    • R2 = hydrogen or C1-C4alkyl, and
    • R3 = aryl, or aryl which is substituted by C1-C4haloalkyl.
    • A particularly preferred compound of formula IV is that wherein
    • R2 = methyl and R3 = 3-trifluoromethylphenyl.
    A particularly preferred compound of formula IV is that, wherein R = pentyl and A = -N=C(CH3)(3-trifluoromethylphenyl).
    Aryl is phenyl or naphthyl, preferably phenyl.
    Entirely surprisingly, it has now been found that the synthesis of the methoximinoglyoxylic acid ester part of formula I and each further reaction in the chloromethyl side chain of this intermediate to a fungicide derived therefrom proceeds in particularly high purity and high yields if the methyl ester is not obtained direct from the o-chloromethylphenylglyoxylic acid amide III by methanolysis but if a long-chain ester is prepared first and the transesterification to the methyl ester is carried out at a later stage of the process.
    The o-chloromethylphenylmethoximinoglyoxylic acid esters of formula I can have the E-configuration, or a Z-configuration, at the imino double bond desirable for the biological activity.
    A very special advantage of the present synthesis of compounds of formula I is that by this process, which proceeds via a long-chain ester, the E-configuration is formed almost exclusively (E/Z ratio higher than 90 : 10).
    Accordingly, suitable alkanols for obtaining intermediates of formula I according to this invention are n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol as well as n-pentanol, n-hexanol, n-heptanol, n-octanol and the corresponding isomers thereof. The C5-C6alkanols in all isomeric forms are preferred, in particular n-pentanol.
    The esterification of compound III or of the corresponding oxime can be carried out in conventional manner under acid reaction conditions, e.g. by adding sulfuric acid or by introducing HCl gas into the reaction medium. The C3-C8alkanol serving the esterification can be used in excess and can also serve as only solvent or diluent. It can also be reacted in admixture with one or more than one inert diluent.
    Suitable diluents are, for example, hydrocarbons or halogenated hydrocarbons, typically hexane, heptane, octane, chloroform, dichloroethane; aromatic hydrocarbons or aromatic halogenated hydrocarbons, typically toluene, xylene, chlorobenzene, dichlorobenzene; or ethers such as dioxane, tetrahydrofuran, diisopropyl ether; ketones such as acetone, methyl isobutyl ketone, cyclopentanone; or mixtures thereof.
    The esterification can be carried out either direct with exclusion of water or under aqueous conditions via prior hydrolysis.
    The hydrolysis of the amide III is preferaby carried out in the presence of stoichiometric amounts of water in the form of the corresponding aqueous concentrated hydrohalic acid, preferably in hydrochloric acid, at a concentration of 25% or more.
    The alkanolysis can be catalysed by small amounts of sulfuric acid or phosphoric acid. Said alkanolysis is carried out in the temperature range from -10° to +120°C, preferably from 0° to 50°C and, particularly preferably, from 20° to 50°C in the presence of the C3-C8alkanol.
    Accordingly, hydrolysis and esterification proceed in one single reaction step of the alkanolysis.
    The reaction of the keto group in the compound of formula III with O-methylhydroxylamine or its salt can be carried out before or after this alkanolysis step of compound III, but is preferably carried out concurrently. It is an essential feature of this invention that the conversion of III to I can be carried out in one single process step.
    The invention also relates to a combined process for the preparation of o-chloromethylphenylmethoximinoglyoxylic acid esters of formula I by
  • a) partial acid saponification of o-chloromethylbenzoyl cyanide of formula II to o-chloromethylphenylglyoxylic acid amide of formula III, and
  • b) reaction of the o-chloromethylphenylglyoxylic acid amide so obtained in any order or concurrently with O-methylhydroxylamine and with a R-OH alcohol, wherein R is C3-C8alkyl, according to the scheme
    Figure 00040001
    Figure 00040002
    • The process of this invention has the surprising advantage of affording the novel amide III in crystalline form in high yield and purity. The use of pure amide III for preparing the compounds of formula I constitutes another advantage of the present process.
    The compounds of formula I are useful as intermediates containing a reactive o-chloromethyl group for preparing pesticides. Such pesticides can be fungicides, insecticides, acaricides, nematicides or herbicides such as are disclosed in EP-A-254426, EP-A-460575, EP-A-463488, EP-A-472300, EP-A-299694, EP-A-253213, WO-95/18799, WO-95/21153 as well as in other publications.
    Working Examples W-1 : Preparation of o-chloromethylpheny glyoxylic acid amide
    Figure 00050001
  • A) 20 g of hydrochloric gas (0.55 mol) are introduced to a suspension of 179.6 g of o-chloromethylbenzoyl cyanide (1 mol) in 400 g of acetic acid over 1 hour. To this mixture are then added 31.8 g of 32% aqueous hydrochloric acid (1.2 mol of water). The suspension is stirred for a further 28 hours at room temperature. The product, which is partly crystallised, is isolated by filtration, washed with 2x50 ml of n-pentanol and 2x50 ml of hexane and then dried. Yield: 89.2 g (45.1%). The mother liquor is recycled in the next batch as diluent.
  • B) 33.1 g of acetic acid are added to a suspension of 179.6 g of o-chloromethylbenzoyl cyanide (1 mol) in 482.9 g of mother liquor of the preceeding batch and then 5 g of hydrochloric gas (0.14 mol) are introduced. 24.3 g of aqueous 32% hydrochloric acid (0.92 mol of water) are added to the reaction mixture at room temperature. The reaction mixture is stirred for 21 hours at room temperature and then filtered. The crystals are washed with pentanol and hexane and then dried. Yield: 172.8 g (87.4%). The mother liquor (486.1 g) is used as diluent in the next batch.
    • W-2 : Preparation of o-chloromethylphenyl-O-methoximinoglyoxylic acid pentyl ester
    Figure 00050002
    Over one hour, 50 g (1.37 mol) of hydrochloric acid gas are introduced to a cooled suspension (0° to -10°C) of 41.8 g of O-methylhydroxylamine hydrochloride (0.5 mol) in 250 g of n-pentanol. The mixture is then heated to about 50°-55°C and a first portion of o-chloromethylphenylglyoxylic acid amide (49.4 g; 0.25 mol) is added. The mixture is stirred for 2 hours at 50°-55°C and then a second portion of o-chloromethylphenylglyoxylic acid amide (49.4 g; 0.25 mol) is added. The mixture is stirred for 24 hours at 50-60°C and then cooled to 20°C amd diluted with 175 ml of water. 159.7 g of a 30% aqueous sodium hydroxide solution are added such that the temperature is kept at 20°-30°C. The organic phase is isolated, dried and concentrated. Yield: 133.1 g (79%).
    The E/Z isomer ratio based on the O-methyloxime side chain is 92.6 : 7.4.
    Replacing n-pentanol in the above process with methanol would result in a very unfavourable E/Z isomer ratio of 83 : 17,
    W-3 : Preparation of 2-[α-{[(α-methyl-3-trilluoromethylbenzyl)imino]oxy}-o-tolyl]glyoxylic acid pentyl ester-O-methyloxime
    Figure 00060001
    87 g of a 30% sodium methylate solution in methanol are added dropwise to a solution of 98.2 g of 3-trifluoromethylacetophenonoxime (0.48 mol) in 200 ml of dimethyl acetamide over 20 minutes. 196 ml of solvent are then distilled off under a slight vacuum at 55°-70°C. After the addition of 1 g of potassium iodide, 150 g of o-chloromethylphenyl-O-methoximinoglyoxylic acid pentyl ester having a purity of 95.9% (0.48 mol) are added over 1 hour at 55°-65°C. After 2 hours, the reaction mixture is added over 30 minutes to a mixture of 400 ml of water and 250 ml of toluene at room temperature, the pH being adjusted to 5 with concentrated hydrochloric acid. The aqueous phase is extracted twice with 150 ml of toluene. The combined organic phases are washed with 150 ml of water. The solvent is distilled off under vacuum at 60°C. 227 g of crude oil are obtained having a 83% content.
    W-3 : Preparation of 2-[α-{[(α-methyl-3-trifluoromethylbenzyl)imino]oxy}-o-tolyl]glyoxylic acid pentyl ester-O-methyloxime
    Figure 00070001
    87 g of a 30% sodium methylate solution in methanol are added dropwise to a solution of 98.2 g of 3-trifluoromethylacetophenonoxime (0.48 mol) in 200 ml of dimethyl acetamide over 20 minutes. 196 ml of solvent are then distilled off under a slight vacuum at 55°-70°C. After the addition of 1 g of potassium iodide, 150 g of o-chloromethylphenyl-O-methoximinoglyoxylic acid pentyl ester having a purity of 95,9% (0.48 mol) are added over 1 hour at 55°- 65°C. After 2 hours, the reaction mixture is added over 30 minutes to a mixture of 400 ml of water and 250 ml of toluene at room temperature, the pH being adjusted to 5 with concentrated hydrochloric acid. The aqueous phase is extracted twice with 150 ml of toluene. The combined organic phases are washed with 150 ml of water. The solvent is distilled off under vacuum at 60°C. 227 g of crude oil are obtained having a 83% content.

    Claims (8)

    1. A process for the preparation of an o-chloromethylphenylmethoximinoglyoxylic acid ester of formula I
      Figure 00080001
      wherein R is C3-C8alkyl, in which process o-chloromethylphenylglyoxylic acid amide of formula III
      Figure 00080002
      is concurrently
      a) oximated with O-methylhydroxylamine and
      b) esterified under acid conditions with a C3-C8alkanol,
      in the presence or absence of a diluent.
    2. A process according to claim 1, which comprises carrying out the reaction in the temperature range from 20°C to 70°C.
    3. A process according to claim 2, which comprises carrying out the reaction in the temperature range from 40°C to 70°C.
    4. A process according to claim 1, which comprises using the C3-C8alkanol reactant as diluent.
    5. A process according to claim 4, which comprises using n-pentanol.
    6. A process for the preparation of an o-chloromethylphenylmethoximinoglyoxylic acid ester of formula I
      Figure 00090001
      wherein R is C3-C8alkyl, which process comprises
      a) partial acid saponification of o-chloromethylbenzoyl cyanide of formula II
      Figure 00090002
      to o-chloromethylphenylglyoxylic acid amide of formula III
      Figure 00090003
      and
      b) conversion of the o-chloromethylphenylglyoxylic acid amide so obtained concurrently with O-methylhydroxylamine and with a C3-C8alkanol.
    7. A process according to claim 6, which comprises using a C5-C6alkanol.
    8. A process according to claim 7, which comprises using n-pentanol.
    EP96939832A 1995-11-29 1996-11-18 Process for the preparation of methoxyminophenylglyoxylic acid derivatives Expired - Lifetime EP0874807B2 (en)

    Applications Claiming Priority (7)

    Application Number Priority Date Filing Date Title
    CH3388/95 1995-11-29
    CH338895 1995-11-29
    CH338895 1995-11-29
    CH45196 1996-02-21
    CH45196 1996-02-21
    CH451/96 1996-02-21
    PCT/EP1996/005057 WO1997019912A1 (en) 1995-11-29 1996-11-18 Process for the preparation of methoxyminophenylglyoxylic acid derivatives

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    EP0874807A1 EP0874807A1 (en) 1998-11-04
    EP0874807B1 true EP0874807B1 (en) 2002-02-20
    EP0874807B2 EP0874807B2 (en) 2006-08-02

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    AT (1) ATE213493T1 (en)
    AU (1) AU7692796A (en)
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    ES2110421T5 (en) * 1990-06-27 2004-12-01 Basf Aktiengesellschaft O-BENCIL-OXIMETERES AND THE PROTECTIVE AGENTS OF THE PLANTS CONTAINING THESE COMPOUNDS.
    US6211413B1 (en) 1998-01-13 2001-04-03 Bayer Aktiengesellschaft Process for the preparation of phenyl alkyl ketones and benzaldehydes
    WO2017024971A1 (en) * 2015-08-12 2017-02-16 沈阳中化农药化工研发有限公司 Unsaturated oximino ether compound and use thereof
    CN106748858B (en) * 2017-01-11 2018-09-28 青岛昌泰和生物科技有限公司 A kind of preparation method of acetaldehyde amide compound

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    PH11991042549B1 (en) * 1990-06-05 2000-12-04
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    GB9018408D0 (en) * 1990-08-22 1990-10-03 Ici Plc Fungicides
    JP3121061B2 (en) * 1991-10-04 2000-12-25 塩野義製薬株式会社 Method for producing intermediate for producing alkoxyiminoacetamides and intermediate used therein
    JP4114948B2 (en) * 1994-06-10 2008-07-09 バイエル、クロップ、サイエンス、アクチェンゲゼルシャフト Process for producing α-methoxyiminocarboxylic acid methylamide and intermediate product thereof

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    WO1997019912A1 (en) 1997-06-05
    AU7692796A (en) 1997-06-19
    DK0874807T4 (en) 2006-11-20
    EP0874807A1 (en) 1998-11-04
    ATE213493T1 (en) 2002-03-15
    HUP9903773A2 (en) 2000-03-28
    JP2000500766A (en) 2000-01-25
    CN1203583A (en) 1998-12-30
    PL326563A1 (en) 1998-09-28
    DE69619402T2 (en) 2003-04-03
    DE69619402D1 (en) 2002-03-28
    ES2173330T3 (en) 2002-10-16
    SK71698A3 (en) 1998-11-04
    MX9804264A (en) 1998-09-30
    ES2173330T5 (en) 2007-03-16
    CZ163098A3 (en) 1998-08-12
    DE69619402T3 (en) 2007-02-08
    EP0874807B2 (en) 2006-08-02
    CA2235587A1 (en) 1997-06-05
    BR9611789A (en) 1999-07-13
    DK0874807T3 (en) 2002-05-13

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